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Tuning energy landscapes and metal-metal interactions in supramolecular polymers regulated by coordination geometry.


ABSTRACT: Herein, we exploit coordination geometry as a new tool to regulate the non-covalent interactions, photophysical properties and energy landscape of supramolecular polymers. To this end, we have designed two self-assembled Pt(ii) complexes 1 and 2 that feature an identical aromatic surface, but differ in the coordination and molecular geometry (linear vs. V-shaped) as a result of judicious ligand choice (monodentate pyridine vs. bidentate bipyridine). Even though both complexes form cooperative supramolecular polymers in methylcyclohexane, their supramolecular and photophysical behaviour differ significantly: while the high preorganization of the bipyridine-based complex 1 enables an H-type 1D stacking with short Pt⋯Pt contacts via a two-step consecutive process, the existence of increased steric effects for the pyridyl-based derivative 2 hinders the formation of metal-metal contacts and induces a single aggregation process into large bundles of fibers. Ultimately, this fine control of Pt⋯Pt distances leads to tuneable luminescence-red for 1 vs. blue for 2, which highlights the relevance of coordination geometry for the development of functional supramolecular materials.

SUBMITTER: Baumer N 

PROVIDER: S-EPMC8179630 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Tuning energy landscapes and metal-metal interactions in supramolecular polymers regulated by coordination geometry.

Bäumer Nils N   Kartha Kalathil K KK   Buss Stefan S   Maisuls Iván I   Palakkal Jasnamol P JP   Strassert Cristian A CA   Fernández Gustavo G  

Chemical science 20210223 14


Herein, we exploit coordination geometry as a new tool to regulate the non-covalent interactions, photophysical properties and energy landscape of supramolecular polymers. To this end, we have designed two self-assembled Pt(ii) complexes <b>1</b> and <b>2</b> that feature an identical aromatic surface, but differ in the coordination and molecular geometry (linear <i>vs.</i> V-shaped) as a result of judicious ligand choice (monodentate pyridine <i>vs.</i> bidentate bipyridine). Even though both c  ...[more]

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